Patent GB-600707-A (GB)
Title: Manufacture of new amide derivatives
IPC: C07C233/00
Filed: 1944-04-06
Abstract: Amide derivatives, containing the grouping <FORM:0600707/III/1> and an aliphatic or cycloaliphatic residue having at least 12 carbon atoms, obtained by reacting a tertiary amine containing at least one hydroxyl group attached to an alkyl chain of at least two carbon atoms with formaldehyde and a carboxylic acid amide or urethane containing at least two carbon atoms joined together and at least one hydrogen atom attached to at least one amide nitrogen atom or with a methylol derivative of such an amide (see Group IV (b)) may be used as dispersing agents.  Typical products are those derived from triethanolamine and the N-methylolamides of oleic, stearic and coconut oil fatty acids.  Numerous other components are specified. The Specification as open to inspection under Sect. 91 relates to products characterised as above, but derived from any amide containing at least two carbon atoms joined together and at least one amido-hydrogen atom including ureas, hydrazides and sulphonamides. This subject-matter does not appear in the Specification as accepted.ALSO:Amide derivatives containing the grouping <FORM:0600707/IV(b)/1> are prepared by reacting a tertiary amine containing at least one hydroxyl group attached to an alkyl residue of at least 2 carbon atoms with formaldehyde and a carboxylic acid amide or urethane containing at least two carbon atoms joined together and at least one hydrogen atom attached to at least one amide-nitrogen atom or with a methylol derivative of such an amide, the reaction being carried out in the absence of primary or secondary amines and, if desired, in the presence of a salt having an alkaline reaction or of an organic acid in a molecular proportion in excess of that of the tertiary amine and when no organic acid as aforesaid is present, in the absence of amine salts.  The reaction is generally effected at a raised temperature and, if desired, in the presence of anhydrous sodium or potassium carbonate or a concentrated water-soluble carboxylic acid such as acetic or formic acid.  When a methylol amide is employed, the water of reaction is preferably removed by means of a current of air or by reacting under reduced pressure.  The formaldehyde may be used in excess.  A hydroxy amine such as triethanolamine may be reacted with one, two of three moles. of the methylol amide.  The products may be converted into salts by means of acetic or formic acid and into quaternary ammonium salts by means of an alkylating agent when there is a free tertiary amino group present.  The products which are stated to be new may be used as water-repelling agents (see Group VIII) and those containing an aliphatic or cycloaliphatic residue of at least 12 carbon atoms may be used as wetting, foaming, dispersing (see Group III), levelling or softening agents and as agents preventing agglomeration of fibrils in working up regenerated cellulose staple fibres into textile material. In examples: (1) the methylolamides of oleic acid, stearic acid and coconut oil fatty acids are each interacted with triethanol amine in the presence of anhydrous sodium carbonate or glacial acetic acid yielding products which, in the form of acetate salts, are softening agents for artificial silk; (2) oleic acid methylol amide is reacted with triethanol amine trihydroxyethyl ether in the presence of sodium carbonate, yielding a product forming foaming solutions in water; (3) oleic acid amide, triethanol amine and paraformaldehyde are reacted together in an atmosphere of nitrogen; the acetate of the product is a softening agent.  Other hydroxy tertiary amines specified are tripropanolamine, tributanolamine, butyl - diethanolamine, di-(hydroxy ethyl) aniline, di - (hydroxyethyl) cyclohexylamine, hydroxyalkyl ethers or polyglycol ethers of these amines, ethers obtained by reacting tertiary hydroxy alkylamines with more than 3 moles. of ethylene oxide and hydroxy alkyl polyalkylene polyamines. Other amido compounds mentioned include amides derived from acetic, acrylic, linoleic, adipic, benzoic, naphthoic, chlor-acetic, chlor-methylbenzoic and glycollic acids, N-substitution products of these amides, for example, methyl-, oxy-ethyl- and di-oxypropyl-lauramide, octadecylurethane and methylene dioctadecylurethane.  Specification 600,706 is referred to.  Samples have been furnished under Sect. 2 (5) of products prepared by reacting benzoic acid methylolamide and octadecylurethane methylolamide respectively with triethanolamine in glacial acetic acid followed by precipitation from aqueous solution by addition of sodium carbonate.  The Specification as open to inspection under Sect. 91 includes the use of any amide containing at least 2 carbon atoms connected together and at least one amido hydrogen atom, reference being made to heterocyclic carboxyamides, cyclic carboxy amides, ureas, hydrazides and sulphonamides, for example, p-stearylamino benzoic acid and abietic acid amides, phthalimide, kiketo-piperazine, mono-methyl urea, mono-phenyl urea and lauric acid hydrazide.  The reaction is not limited to the conditions specified above.  This subject-matter does not appear in the Specification as accepted.ALSO:Amide derivatives containing the grouping -CO.N-CH2OC­ and prepared by reacting a tertiary amine containing at least one hydroxyl group attached to an alkyl residue of at least 2 carbon atoms with formaldehyde and a carboxylic acid amide or urethane containing at least two carbon atoms joined together and at least one hydrogen atom attached to at least one amide-nitrogen atom or with a methylol derivative of such an amide, under specified conditions (see Group IV (b)), and said derivatives which have been converted into salts by means of acetic or formic acid and into quaternary ammonium salts by means of an alkylating agent when there is a free tertiary amino group present, may be used as textile assistants and those containing an aliphatic or cycloaliphatic residue having at least 12 carbon atoms may be used as wetting, foaming, dispersing, levelling or softening agents and as agents preventing agglomeration of fibrils in working up regenerated cellulose staple fibres into textile material.  Thus, according to examples: (1) the methylolamides of oelic acid, stearic acid and coconut oil fatty acids are each interacted with triethanolamine in the presence of anhydrous sodium carbonate or glacial acetic acid yielding products which, in the form of acetate salts, are softening agents for artificial silk; (2) oleic acid methylol amide is reacted with triethanol-amine trihydroxyethyl ether in the presence of sodium carbonate yielding a product forming foaming solutions in water; (3) oleic acid amide, triethanolamine and paraformaldehyde are reacted together in an atmosphere of nitrogen, the acetate of the product being a softening agent.  Further compounds of the above type having similar properties may be derived from tripropanolamine, tributanolamine, butyl - diethanolamine, di(hydroxy ethyl) aniline, di(hydroxyethyl)cyclohexylamine, hydroxyalkyl ethers or polygycol ethers of these amines, ethers obtained by reacting tertiary hydroxy alkylamines with more than 3 moles of ethylene oxide and hydroxyl alkyl polyalkylene polyamines and, for example, amides derived from acetic, acrylic, linoleic, adipic, benzoic, naphthoic, chlor-acetic, chlor-methyl benzoic and glycollic acids, N-substitution products of these amides such as methyl-, oxyethyl- and dioxypropyl-lauramide octadecylurethane and methylene dioctadecylurethane. Specification 600,706 is referred to. The Specification as open to inspection under Sect. 91 refers to wetting agents of the above type derived from any amide containing at least 2 carbon atoms connected together and at least one amido hydrogen atom, reference being made to heterocyclic carboxyamides, cyclic carboxy amides, ureas, hydrazides and sulphonamides.  This subject-matter does not appear in the Specification as accepted.